•We report an efficient iron corrole–catalyzed oxidations using iodobenzene diacetate.•We examine the reaction conditions and scope, and demonstrate the synthetic utility.•We report the mechanistic studies including competition and spectra studies.•We propose a high-valent iron(V)-oxo intermediate as the active oxidant.

The electron-deficient iron(III) corrole complex catalyzes the efficient oxidation of hydrocarbons using PhI(OAc)2 as an mild oxygen source. The catalyst stability against degradation was much enhanced owing to the mild oxidizing ability of PhI(OAc)2. Excellent selectivity and high catalytic efficiency (with up to 1400 TON) have been achieved in alkene epoxidations. This promising oxygen transfer process is mechanistically rationalized in terms of a putative high-valent iron(V)-oxo species as the active oxidant.